5-Nitrothiazolyl-2-azophenyl disperse dyes

ABSTRACT

This invention relates to monoazo compounds of the formula I, ##STR1## in which R 1  signifies a hydrogen atom, an alkyl radical or an unsubstituted or substituted phenyl radical, 
     Each of R 2  and R 3  signifies a hydrogen atom, a cycloalkyl radical, an alkenyl radical or an unsubstituted or substituted alkyl radical, with the proviso that when one of R 2  and R 3  signifies a hydrogen atom, the other has a significance other than hydrogen, 
     R 4  signifies an α- or β-chloro- or bromoethyl radical, 
     R 5  signifies a hydrogen atom or a methoxy or ethoxy radical, and 
     X signifies a group of the formula --CO--or --CO--O--. 
     These compounds are useful as disperse dyes, particularly for the exhaust dyeing, pad dyeing and printing of synthetic and semi-synthetic hydrophobic materials such as linear and aromatic polyesters, cellulose acetates and polyamides. The dyeings exhibit good fastness to light, heat treatments, wet treatments, solvents, lubricants, rubbing, cross-dyeing, ozone, gas fumes and chlorine.

The present invention relates to monoazo compounds of low solubility inwater, their production and use.

More particularly, the present invention provides monoazo compounds offormula I, ##STR2## in which R₁ signifies a hydrogen atom, a (C₁₋₆)alkyl radical, an unsubstituted phenyl radical or a phenyl radicalsubstituted by one cyano group and/or by up to three substituentsselected from the group consisting of chlorine and bromine atoms,

Each of R₂ and R₃, independently, signifies a hydrogen atom, a (C₂₋₆)alkenyl radical, a (C₅₋₇) cycloalkyl radical, an unsubstituted (C₁₋₆)alkyl radical or a (C₁₋₆) alkyl radical substituted by a cycloalkyl orcycloalkyl radical, each of which contains from 5 to 8 carbon atoms,with the proviso that when one of R₂ and R₃ signifies a hydrogen atom,the other has a significance other than hydrogen,

R₄ signifies an α- or β-chloro- or bromo-ethyl radical,

R₅ signifies a hydrogen atom or a methoxy or ethoxy radical, and

X signifies a group of the formula --CO-- or --CO--O--.

The present invention further provides a process for the production ofcompounds of formula I, as defined above, comprising coupling adiazotized amine of formula II, ##STR3## in which R₁ is as definedabove,

with a compound of formula III, ##STR4## in which X, R₂, R₃, R₄ and R₅are as defined above.

The coupling reaction may be carried out according to conventionalmethods. The coupling reaction is conveniently carried out in an acid,optionally buffered, medium, e.g. at a pH of less than 5. Suitablereaction temperatures are below 20° C, preferably between -5° and +5° C.Suitable buffering agents include alkali metal salts of low molecularweight alkane acids, for example of acetic or propionic acid. Thepreferred buffering agent is sodium acetate.

The diazotization of the amine of formula II, as defined above, may beaccomplished by known methods.

The compounds of formula II and III are known or may be prepared byknown methods.

In the compounds of formula I, as defined above, where R₁ signifies asubstituted phenyl radical, such radical is preferably monosubstituted.

Preferred compounds of formula I include those of formula I', ##STR5##in which R₁ ' signifies a hydrogen atom, a (C₁₋₂) alkyl radical, anunsubstituted phenyl radical or a phenyl radical substituted by achlorine or bromine atom or by a cyano group,

each of R₂ ' and R₃ ', independently, signifies a (C₁₋₄)alkyl,(C₂₋₄)alkenyl, cyclohexyl, cyclohexyl(C₁₋₄)alkyl orcyclohexenyl(C₁₋₄)alkyl, and

R₄ and X are as defined above.

In the compounds of formula I or I', where any of R₂ and R₃ or R₂ ' andR₃ 40 signifies an alkenyl radical, such radical is preferably an allylradical.

The preferred compounds of formula I', are those of formula I", ##STR6##in which R₁ " signifies a hydrogen atom or a methyl or phenyl radical,

each of R₂ " and R₃ ^("), independently, signifies an alkyl radical of1, 2, 3 or 4 carbon atoms,

R₄ ' signifies β-chloroethyl or β-bromoethyl, and

X is as defined above.

In the compounds of formula I, I' and I" those compounds where X is aradical of formula --CO-- are preferred.

The preferred compounds of formula I" are those of formula I'" ,##STR7## in which R₁ '" signifies a hydrogen atom or a methyl radical,

each of R₂ '" and R₃ '", independently, signifies an alkyl radical of 2,3 or 4 carbon atoms.

The compounds of the invention are useful as disperse dyes. They areparticularly useful for exhaust dyeing, pad dyeing or printing ofsubstrates consisting of or comprising synthetic or semisyntheticorganic fibres of high molecular weight and hydrophobic character. Thesubstrate may be, for example, in loose fibre, yarn or fabric form. Thecompounds are especially suitable for dyeing or printing substratesconsisting of or comprising linear or aromatic polyesters, cellulose21/2 acetate, cellulose triacetate and synthetic polyamide fibres.

It has been found that the compounds of formula I which contain an α- orβ-chloroethyl or bromoethyl group are notably stable under dyeingconditions, particularly in high temperature processes.

The compounds of formula I, as defined above, may be converted intodyeing preparations according to known methods, for example, by grindingin the presence of dispersing agents and/or fillers, optionally withsubsequent vacuum or atomizer drying. The preparations are dispersed ina suitable volume of water for application by exhaust dyeing, pad dyeingor printing methods.

Conventional dyeing and printing methods may be employed, for example,the process described in French Patent No. 1,445,371 may be used.

The dyeings obtained have notable all-round fastness, for example,notable fastness to light, thermofixation, sublimation and pleating.They have notable wet fastness properties, for example fastness towater, sea water, washing, perspiration and solvents, including drycleaning liquors, and to lubricants, rubbing, cross-dyeing, ozone, gasfumes and chlorine. The dyes are stable to the pre-cure and post-curepermanent press finishing processes and to soil release finishes. Thedyes reserve wool and cotton, are stable to reducing action in thedyeing of textiles containing wool, are stable to high temperatureprocesses and their dischargeability is good.

The following Examples serve to further illustrate the invention. In theExamples all parts are by weight and the temperatures are in degreescentigrade.

EXAMPLE 1

14.5 Parts of 2-amino-5-nitrothiazole are slowly added at 0°-5° to amixture consisting of 107 parts of nitrosyl sulphuric acid (produced bydissolution of 7 parts of sodium nitrite in 100 parts of concentratedsulphuric acid), 85 parts of glacial acetic acid and 15 parts ofpropionic acid. A mixture consisting of 85 parts of glacial acetic acidand 15 parts of propionic acid is added at 0°-5° to the resultingmixture. The mixture is subsequently stirred at 0°-5° over the course of3 hours. A solution of 25.5 parts of3-(β-chloropropionylamino)-1-N,N-diethylaminobenzene in 85 parts ofglacial acetic acid and 15 parts of propionic acid is added dropwise.The resulting coupling mixture is stirred at 0°-5° over the course of 3hours. The reaction mixture is then poured with stirring into a mixtureconsisting of 200 parts of water and 500 parts of ice, whereupon the dyeof the formula ##STR8## precipitates. The dye is filtered off, washedwith water until it is free from acid and salt and then dried. Theresulting dye is stable to high tempertures and dyes synthetic fibres inblue shades with good fastness properties. The dyes of the followingTables are produced in analogy with the process described in Example 1.

                                      TABLE 1                                     __________________________________________________________________________    General formula                                                               __________________________________________________________________________     ##STR9##                                                                     Exp.                        Shade on                                          No.                                                                              R.sub.1                                                                              R.sub.2  R.sub.3  polyester                                         __________________________________________________________________________    2  H      CH.sub.2 CH.sub.2 CH.sub.3                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                             blue                                              3  CH.sub.3                                                                              "        "        "                                                4   "     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                     "                                                5  H       "        "        "                                                6  C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         "                                                7   "     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      "                                               8  C.sub.6 H.sub.5                                                                      C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         "                                                9  CH.sub.3                                                                             n-C.sub.4 H.sub.9                                                                      H         "                                                10                                                                                ##STR10##                                                                           C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                            11 CH.sub.3                  "                                                           "        "        "                                                __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    General formula:                                                              __________________________________________________________________________     ##STR11##                                                                    Exp.                          Shade on                                        No.                                                                              R.sub.1                                                                           R.sub.2 R.sub.3 R.sub.4                                                                              polyester                                       __________________________________________________________________________    12 H   CH.sub.2 CH.sub.3                                                                     CH.sub.2 CH.sub.3                                                                      ##STR12##                                                                           blue                                            13 CH.sub.3                                                                           "       "       "      "                                              14 C.sub.6 H.sub.5                                                                    "       "       "      "                                              15  "   "       "      CH.sub.2 CH.sub.2 Cl                                                                  "                                              16  "   "       "      CH.sub.2 CH.sub.2 Br                                                                  "                                              17 H    "       "       "      "                                              18 CH.sub.3                                                                           "        "      "      "                                              19  "   "       "                                                                                     ##STR13##                                                                            "                                              20 H    "       "       "      "                                              21 C.sub.2 H.sub.5                                                                   CH.sub.2 CH.sub.2 CH.sub.3                                                            CH.sub.2 CH.sub.2 CH.sub.3                                                            CHClCH.sub.3                                                                          "                                              22  "  n-C.sub.4 H.sub.9                                                                     n-C.sub.4 H.sub.9                                                                     CH.sub.2 CH.sub.2 Br                                                                  "                                              23  "  C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                        "      "                                              __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                        General formula:                                                              ______________________________________                                         ##STR14##                                                                    Exp.                                   Shade on                               No.   R.sub.1  R.sub.2   R.sub.3  Y    polyester                              ______________________________________                                        24    H        CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.3                                                                      Cl   blue                                   25    CH.sub.3  "         "       Cl    "                                     26    C.sub.6 H.sub.5                                                                         "         "       Cl    "                                     27     "        "         "       Br    "                                     28    CH.sub.3  "         "       Br    "                                     29    H         "         "       Br    "                                     30    H        CH.sub.3  CH.sub.3 Br    "                                     31    H         "         "       Cl    "                                     32    C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                        Cl    "                                     33     "       n-C.sub.4 H.sub.9                                                                       n-C.sub.4 H.sub.9                                                                      Cl    "                                     34     "       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                        Br    "                                     ______________________________________                                    

                                      TABLE 4                                     __________________________________________________________________________    General formula:                                                              __________________________________________________________________________     ##STR15##                                                                    Exp.                                   Shade on                               No.                                                                              R.sub.1                                                                              R.sub.2                                                                             R.sub.3   R.sub.4                                                                              X     polyester                              __________________________________________________________________________    35 H      CH.sub.2 CH.sub.3                                                                   CH.sub.2CHCH.sub.2                                                                      CH.sub.2 CH.sub.2 Cl                                                                 CO    blue                                   36 CH.sub.3                                                                              "     "         "     COO    "                                     37  "      "                                                                                   ##STR16##                                                                               "      "     "                                     38 H      CH.sub.3                                                                             ##STR17##                                                                               "     CO     "                                     39 H      CH.sub.2 CH.sub.3                                                                    ##STR18##                                                                               "     CO     "                                     40 CH.sub.3                                                                              "     "         "     COO    "                                     41                                                                                ##STR19##                                                                            "    CH.sub.2 CH.sub.3                                                                        "      "     "                                     42                                                                                ##STR20##                                                                            "     "         "     CO     "                                     43                                                                                ##STR21##                                                                            "     "                                                                                       ##STR22##                                                                            "     "                                     44 H       "                                                                                   ##STR23##                                                                               "     CO     "                                     45 CH.sub.3                                                                              "     "         "     COO    "                                     46 H       "                                                                                   ##STR24##                                                                              CH.sub.2 CH.sub.2 Cl                                                                 CO     "                                     47 H       "     "        CH.sub.2 CH.sub.2 Br                                                                  "     "                                     __________________________________________________________________________

The dyes of the following Table 5 correspond to formula I.

                                      TABLE 5                                     __________________________________________________________________________                                                Shade                             Exp.                                        on poly-                          No.                                                                              R.sub.1                                                                             R.sub.2                                                                            R.sub.3   R.sub.4                                                                              R.sub.5                                                                              X     ester                             __________________________________________________________________________    48 H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         CH.sub.2 CH.sub.2 Cl                                                                 OCH.sub.3                                                                            CO    blue                              49 CH.sub.3                                                                             "    "         "      "     CO     "                                50  "     "    "         "     OCH.sub.2 CH.sub.3                                                                   CO     "                                51  "     "    "         "      "     COO    "                                52 H      "    "         "      "      "     "                                53 H      "    "         "      "     CO     "                                54 H     n-C.sub.3 H.sub.7                                                                  n-C.sub.3 H.sub.7                                                                        "     OCH.sub.3                                                                            CO     "                                55 H     n-C.sub.4 H.sub.9                                                                  n-C.sub.4 H.sub.9                                                                        "      "     CO     "                                56 H     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                          ##STR25##                                                                            "     CO     "                                57 H     n-C.sub.4 H.sub.9                                                                  H         CH.sub.2 CH.sub.2 Cl                                                                  "     CO     "                                58 CH.sub.3                                                                             "   H          "      "     COO    "                                59 H     C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                       "      "     CO     "                                60 H      "                                                                                  ##STR26##                                                                               "      "     CO     "                                61 H      "                                                                                  ##STR27##                                                                               "      "     CO     "                                62 H     CH.sub.3                                                                           CH.sub.3   "      "     CO     "                                63 C.sub.6 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                          "      "     CO     "                                64 H     CH.sub.3                                                                            ##STR28##                                                                              CH.sub.2 CH.sub.2 Cl                                                                 OCH.sub.3                                                                            CO     "                                65                                                                                ##STR29##                                                                          C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                          "     OCH.sub.2 CH.sub.3                                                                   CO     "                                66                                                                                ##STR30##                                                                           "    "                                                                                       ##STR31##                                                                            "     CO     "                                67                                                                                ##STR32##                                                                           "    "        CH.sub.2 CH.sub.2 Br                                                                 OCH.sub.3                                                                            CO     "                                68 H      "    "        CH.sub.2 CH.sub.2 Cl                                                                  "     COO    "                                69 CH.sub.2 CH.sub.3                                                                    "    "         "      "      "     "                                70  "     "    "         "      "     CO     "                                71  "     "    "         "     OCH.sub.2 CH.sub.3                                                                   CO     "                                __________________________________________________________________________

EXAMPLE A

7 Parts of the dye produced as described in Example 1, 4 parts of sodiumdinaphthyl methane disulphonate, 4 parts of sodium cetyl sulphate and 5parts of anhydrous sodium sulphate are ground in a ball mill for 48hours to give a fine powder.

1 Part of the powder is dispersed in a small amount of water and thedispersion is added through a sieve to a bath of 4000 parts of watercontaining 3 parts of sodium lauryl sulphate. The liquor ratio is 1:40.At 40°-50°, 100 parts of a scoured fabric of polyester fibre are enteredinto this dye bath, which is then set with an emulsion of 20 parts of achlorinated benzene in water. The bath is raised slowly to 100° and thefabric dyed for 1 to 2 hours at 95°-100°. The fabric is dyed inbrilliant blue shades, is washed, soaped, washed again and dried. Thelevel dyeing has good fastness to light, cross dyeing, washing, water,sea water, perspiration, sublimation, gas fumes, thermofixation,pleating and permanent press finishing.

What is claimed is:
 1. A compund of the formula ##STR33## wherein R₁ ishydrogen, alkyl of 1 to 6 carbon atoms or ##STR34## wherein each Y isindependently chloro or bromo,m is 0 or 1, and n is 0 to 3, each of R₂and R₃ is independently hydrogen, alkenyl of 2 to 6 carbon atoms,cycloalkyl of 5 to 7 carbon atoms, alkyl of 1 to 6 carbon atoms or alkylof 1 to 6 carbon atoms monosubstituted by cycloalkyl of 5 to 8 carbonatoms or cycloalkenyl of 5 to 8 carbon atoms, with the proviso that atleast one of R₂ and R₃ is other than hydrogen, R₄ is chloroethyl orbromoethyl, R₅ is hydrogen, methoxy or ethoxy, and X is --CO-- or--CO--O--.
 2. A compound according to claim 1 wherein X is --CO--.
 3. Acompound according to claim 1 having the formula ##STR35## wherein R₁ 'is hydrogen, alkyl of 1 or 2 carbon atoms, phenyl or phenylmonosubstituted by chloro, bromo or cyano,each of R₂ ' and R₃ ' isindependently alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbonatoms, cyclohexyl, alkyl of 1 to 4 carbon atoms monosubstituted bycyclohexyl or alkyl of 1 to 4 carbon atoms monosubstituted bycyclohexenyl, R₄ is chloroethyl or bromoethyl, and X is --CO-- or--CO--O--.
 4. A compound according to claim 3 whereineach of R₂ ' and R₃' is independently alkyl of 1 to 4 carbon atoms, allyl, cyclohexyl,alkyl of 1 to 4 carbon atoms monosubstituted by cyclohexyl or alkyl of 1to 4 carbon atoms monosubstituted by cyclohexenyl.
 5. A compoundaccording to claim 3wherein X is --CO--.
 6. A compound according toclaim 3 having the formula ##STR36## wherein R₁ " is hydrogen, methyl orphenyl,each of R₂ " and R₃ " is independently alkyl of 1, 2, 3 or 4carbon atoms, R₄ ' is β-chloroethyl or β-bromoethyl, and X is --CO-- or--CO--O--.
 7. A compound according to claim 6 wherein X is --CO--.
 8. Acompound according to claim 6 having the formula ##STR37## wherein R₁ '"is hydrogen or methyl, andeach of R₂ '" and R₃ '- is independently alkylof 2, 3 or 4 carbon atoms.
 9. A compound according to claim 3 having theformula ##STR38## wherein R₁ '" is hydrogen or methyl,each of R₂ "" andR₃ "" is n-alkyl of 2 to 4 carbon atoms and R₄ " is chloroethyl.
 10. Thecompound according to claim 9 having the formula ##STR39##
 11. Thecompound according to claim 9 having the formula ##STR40##
 12. Thecompound according to claim 9 having the formula ##STR41##
 13. Thecompound according to claim 9 having the formula ##STR42##
 14. Thecompound according to claim 9 having the formula ##STR43##